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Pioneering Heterogeneous Organometallic-Mediated Electrocatalytic Reactions (PiHOMER)
Start date: Aug 1, 2012, End date: Jul 31, 2017 PROJECT  FINISHED 

This project pioneers the use of Heterogeneous Organometallic Mediated Electrocatalytic Reactions (HOMER) and our understanding thereof. Examples of electron transfer activation of C-H, C-Halide bonds and cycloaddition reactions of unactivated olefins are sought that are catalysed by appropriate combinations of electrochemically generated odd-electron (17-electron) organometallic “radical” complexes and 7-electron perhalogenated arylborane Lewis acidic radical species. The electrochemistry of a series of Group VI-IX transition metal half-sandwich complexes, empirically “Cp’M(CO)n” (where n=2 or 3 in order to satisfy the metal centre’s demand for an 18-electron configuration; Cp’ = η5-C5H4CO2R, where R = Me) will be explored both in the solution phase and covalently attached to an electrode surface. These chemically modified “HOMER platforms” will be exposed to a wide variety of hydrocarbon feedstocks during electrolysis, and evidence of C-H/C-halide bond activation sought. Optimization of the HOMER catalysts will be attempted by systematically varying the ligands within the complex.This includes a study of the electrochemistry of Group IV to VIII transition metal complexes bearing at least 1 borylcyclopentadienyl ligand that incorporates a Lewis acid group into the HOMER catalyst.Novel perchlorinated arylboranes, (C6F5)3-nB(C6Cl5)n n=1-3 “BArCl” recently reported by the PI and co-workers will be examined for their activity in Frustrated Lewis Pair (FLP) activation of small molecules. An “electrochemical-FLP” (e-FLP) system will be pioneered by electrochemically oxidising the [BArClH]- products of FLP activation of H2 to produce [BArClH]• intermediates - a source of “H•”. The activation of small molecules via the e-FLP concept will be explored, and combined with suitable HOMER catalysts in an effort to generate e-FLP-HOMER systems capable of undergoing an electrocatalytic analogue of the Fischer-Tropsch reaction.

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